Semiconductor device and method of manufacturing same

ABSTRACT

A method of manufacturing a semiconductor device comprises forming a trench in a semiconductor substrate, forming a first insulating film having a first recessed portion in the trench, forming a coating film so as to fill the first recessed portion therewith, transforming the coating film into a second insulating film, planarizing the second insulating film to expose the first insulating film and the second insulating film, removing at least the second insulating film from the first recessed portion to moderate an aspect ratio for the first recessed portion formed in the trench, thereby forming a second recessed portion therein, and forming a third insulating film on a surface of the semiconductor substrate so as to fill the second recessed portion therewith.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is based upon and claims the benefit of priority fromprior Japanese Patent Application No. 2005-155806, filed May 27, 2005,the entire contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a semiconductor device and a method ofmanufacturing the same and, in particularly, to an STI structure havinga preferable surface shape and a method of manufacturing the same.

2. Description of the Related Art

An element isolation technique is known as one of the importanttechniques to achieve a high integration density of an LSI. In theisolation technique, a shallow trench isolation (STI) structure ismainly used. However, although, at the present, a ratio of a trenchwidth to a trench depth (aspect ratio) increases, STI filling cannot beeasily performed without forming a void or a seam in a TEOS/O₃ filmobtained by a conventional normal-pressure CVD method, an HDP-TEOS filmobtained by a plasma CVD method, or the like. Especially, in the STIfilling of an NAND flash memory, a silicon oxide film must be filled inthe form of a high aspect and taperless STI shape as compared to a logicdevice. For this reason, it is difficult from 90-70-nm-width generationthat a high density plasma (HDP) single-layer oxide film, which does notpose any problem in 130-nm-width generation, is once filled in the STIstructure.

As a countermeasure against the above problem, an STI filling techniqueusing a coating film has been developed. For example, after an HDP filmis formed in a trench having a depth of 350 to 450 nm from a floatinggate surface to an STI bottom, a coating film of a perhydro-silazanepolymer (Polysilazane to be referred as PSZ hereinafter) solution isformed and etched back by devising wet etching, so that a level of STIfilling may be controlled.

However, in a trench having a narrow STI width, a wet etching rate ofthe PSZ film is considerably higher than that of the HDP film. Inparticular, when an etching solution containing hydrogen fluoride isused for the STI structure having a width of about 90 nm, a largeetching rate difference of 2.5 times or more is generated. Therefore,the PSZ film is mainly etched, and the HDP film filled in the STI trenchof the semiconductor substrate is thinly left on a side surface of afloating gate (FG) formed through a tunnel insulating film, or the HDPfilm is partially left in the shape of a taper on the side surface ofthe floating gate.

Depression of the STI filling material surface is caused by the etchingrate difference because the PSZ film is not sufficiently transformedinto SiO₂. In order to decrease the etching rate of the PSZ film in thestep of densifying the SiO₂ film, a method of planarizing and thendensifying the SiO₂ film is proposed. However, even in this method, whenthe STI trench width is about 100 nm or less, oxygen (O₂) required tosufficiently transform the PSZ film into the SiO₂ film is not deeplysupplied to the STI trench, and the situation of wet etchingcontrollability is still difficult.

In order to secure the drivability of the control gate on the floatinggate side surface, an improved shape (tapered shape having a thin HDPfilm) is very difficult to be formed in a wafer plane or between waferplanes with good controllability. For this reason, even though a controlgate (CG) is formed on the floating gate and the filled HDP film throughan ONO film and an interlayer insulating film is formed on the controlgate, a ratio (coupling ratio) of a coupling capacitance C2 between thefloating gate (FG) and the control gate (CG) and a coupling capacitanceC1 between the floating gate (FG) and the substrate may fluctuate tocause a decrease in yield.

Furthermore, when a fine device structure advances, the STI filledsurface depressed in a concave shape is close to the level of a tunneloxide film to cause deterioration of a breakdown voltage between thesubstrate and the control gate. In this manner, at the present, an STItechnique of 90-70-nm-width generation or later is not established, anda technique which can easily control an STI filling level and theplanarity is demanded.

As a technique that fills the trench with the HDP film, the followingtechnique is disclosed in Jap. Pat. Appln. KOKAI Publication No.2002-208629. That is, the HDP oxide film is coated on the substratesurface until a trench opening is sealed, and an oxide film near theopening is removed. Thereafter, an HDP oxide film is coated again tofill the trench with the HDP oxide film.

BRIEF SUMMARY OF THE INVENTION

According to a first aspect of the invention, a method of manufacturinga semiconductor device comprises: forming a trench in a semiconductorsubstrate; forming a first insulating film having a first recessedportion in the trench; forming a coating film so as to fill the firstrecessed portion therewith; transforming the coating film into a secondinsulating film; planarizing the second insulating film to expose thefirst insulating film and the second insulating film; removing at leastthe second insulating film from the first recessed portion to moderatean aspect ratio for the first recessed portion formed in the trench,thereby forming a second recessed portion therein; and forming a thirdinsulating film on a surface of the semiconductor substrate so as tofill the second recessed portion therewith.

According to a second aspect of the invention, a method of manufacturinga semiconductor device comprises: forming a trench in a semiconductorsubstrate; forming a first insulating film having a recessed portion inthe trench; planarizing an upper side of the first insulating film by aCMP method using a slurry; removing at least the slurry remaining in therecessed portion of the first insulating film by a chemical solution tomoderate an aspect ratio for the recessed portion formed in the firstinsulating film; and forming a second insulating film on a surface ofthe semiconductor substrate so as to fill the recessed portiontherewith.

According to a third aspect of the invention, a semiconductor deviceincludes active regions each being isolated by a trench and having atunnel insulating film for providing each memory cell and a floatinggate provided on the tunnel insulating film, the semiconductor devicecomprises; a first CVD oxide film filled in the trench to at least alevel of the floating gate and a second CVD oxide film provided on thefirst CVD oxide film.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plan view typically showing an ordinary flash memory cellstructure;

FIG. 2 is a II-II sectional view of FIG. 1;

FIG. 3 is a III-III sectional view of FIG. 1;

FIGS. 4A to 4O are sectional views schematically showing some of thesteps in manufacturing an STI structure according to a first embodiment;

FIGS. 5A to 5D are sectional views schematically showing some of thesteps in manufacturing an STI structure according to a secondembodiment;

FIGS. 6A to 6C are sectional views schematically showing some of thesteps in manufacturing an STI structure according to a third embodiment;and

FIGS. 7A to 7D are sectional views schematically showing some of thesteps in manufacturing an STI structure according to a fourthembodiment.

DETAILED DESCRIPTION OF THE EMBODIMENTS

A method of manufacturing a semiconductor device according to a firstembodiment will be described with reference to FIGS. 4A to 4O. FIG. 1 isa plan view of a NAND flash memory cell structure using an STI structureknown by persons skilled in the art, and FIGS. 2 and 3 are a II-IIsectional view and a III-III sectional view of FIG. 1, respectively.

More specifically, commonly, memory cells such as M1 to M8, each havinga source/a drain are arranged between select lines S1 and S2 in a matrixof rows and columns, and a word line WL and a bit line BL (omitted) areprovided. As shown in FIG. 2, each memory cell includes a tunnel oxidefilm 11 composed of a silicon oxide film, a floating gate (FG)constituted by two polysilicon films 12 and 13, a control gate (CG) 23formed through an ONO film 22, and an interlayer insulating film 24,which are formed on a semiconductor substrate 10. The memory cells areelectrically isolated from each other by HDP films 18 buried intrenches. As shown in FIG. 3, a source of a select transistor isconnected to a wiring layer 29 through a plug 28.

It is difficult that the STI structure is practically formed by a CVDmethod using the HDP film or the like when filling in the STI having awidth of about 90 nm or less is realized at low cost. The STI structureobtained by the filling technique using the coating solution which isattempted in a development stage at the present and the STI structureobtained by the filling technique using the coating method shown in theembodiment are different from each other in the following points.

More specifically, (a) in an STI structure having a width of 90 nm orless, an STI filling material surface is flat and is uniform to apattern width. (b) A step coverage generated in formation of the fillingmaterial is caused to be generated outside and above the STI to performa planarizing process, and etching back is performed by an etchingprocess until an FG side wall portion in the STI is exposed. (c) At thistime, a filling material in at least a region to be etched back has anuniform etching rate in the entire region.

A method of forming an STI structure using such a coating film will bedescribed below. FIGS. 4A to 4L are sectional views of manufacturingsteps corresponding to FIG. 1. In particular, the sectional viewscorrespond to a region having a narrow STI width (≦90 nm) correspondingto a dotted-line portion in FIG. 2. In this case, the explanationnarrows down to the step of forming an STI structure. However, beforethis process is performed, formation of a sacrificial oxide film,channel ion implantation, removal of the sacrificial oxide film,formation of a gate oxide film, formation of a gate electrode, andformation of a source/drain layers are performed. After the process iscarried out, formation of interlayer insulating films, formation ofcontacts, and formation of wiring layers are performed in the samemanner as described above.

A process for manufacturing an STI structure of 90-nm generation will bedescribed below. More specifically, as shown in FIG. 4A, an SiO₂ film 11is formed on a silicon (100) substrate 10 to a thickness of, e.g., about10 nm, and polycrystalline silicon films 12 and 13 are formed on theresultant structure by an LP-CVD method to a thickness of 150 nm.

As shown in FIGS. 4B and 4C, an Si₃N₄ film 14 is formed to a thicknessof about 100 nm. The Si₃N₄ film 14, the polysilicon films 13 and 12, theSiO₂ film 11, and the silicon substrate 10 are processed through a masklayer 15 to form a trench 17 for isolation STI to a depth of, e.g.,about 450 nm.

In FIG. 4C, although not shown, the side surfaces of the trench 17 areoxidized by using an ordinary thermal oxidation method to form a thermaloxide film having a thickness of about 3 nm. This is formed to protectan exposed portion at a tunnel oxide film end. A uniform high-qualityoxide film may also be formed on the silicon side wall of STI by usingradical oxidation or the like independently of the wafer orientation. Atthis time, the side surface of the Si₃N₄ film 14 may be slightlyoxidized.

As shown in FIG. 4D, an HDP film 18 of a CVD oxide film is deposited forall the trenches 17 in the wafer by an HDP-CVD method such that a heightfrom the silicon interface under the floating gate to the bottom of thefilled HDP is, e.g., 80 nm or more. At this time, in the HDP film 18,the STI opening may be filled to form a void in the trench before theSTI trench is completely filled. For this reason, the deposition processmust be controlled. Therefore, a first recessed portion 181 which isleft in the HDP film 18 without completely filling the trench is formed.As shown in FIG. 4D, the surface of the bottom of the first recessedportion 181 is not always flat, and it may be corrugated ordiscontinuous. The side surfaces of the first recessed portion 181 arenot always vertical in shape. That is, the side surfaces may havestep-like shapes or may be overhang.

As shown in FIG. 4E, a coating type solution 19 is deposited on thesubstrate surface by a coating method to completely fill the structure.For example, the coating film is formed under such a coating conditionthat the coating film has a thickness of about 600 nm. In this case, forexample, the PSZ is deposited by a spin coating method, and a bakingstep is performed at 150° C. for about 3 minutes in a coating apparatusto vaporize the solvent.

As shown in FIG. 4F, for example, the PSZ film on the Si₃N₄ film 14 isselectively removed by a CMP method. However, when the baked PSZ film issoft and beside the PSZ film contains a large amount of nitride, anetching selectivity between the PSZ film and the Si₃N₄ film cannot beeasily obtained. Therefore, the PSZ film must be cured to some extent.In order to transform the PSZ film 19 into a SiO₂ (silica) film 191, ahigh-temperature heat treatment (curing) is then performed in a watervapor atmosphere before the CMP process. This process can be explainedby the following chemical formula:

(SiH₂NH)_(n-)+2nO→nSiO₂+nNH₃

More specifically, the PSZ film reacts with oxygen (O) generated bydecomposition of water vapor (H₂O+O₂) to produce SiO₂ and NH₃ (ammoniagas), so that the PSZ film is efficiently transformed into SiO₂(silica). At this time, since an active area is covered with the SiNfilm 14, it is not oxidized. The chemical reaction described aboveproceeds from the surface side of the PSZ. It is confirmed that the PSZfilm coated on a wafer with a planar structure to a thickness of about600 nm can be transformed into an SiO₂ film by combustion oxidation (BOXoxidation) performed at, e.g., 850° C. in a water vapor atmosphere forabout 30 minutes.

Furthermore, a heat treatment is carried out at about 850° C. in anoxidizing atmosphere or an inert gas atmosphere. The HDP film formed asa lower layer is then densified and gases such as NH₃, H₂O, or the likeremaining in the SiO₂ film obtained by changing the PSZ film formed asan upper layer are discharged to perform a densifying treatment, wherebythe PSZ film is transformed into the SiO₂ film 191 having a higherdensity. At this time, since the active area is covered with the SiNfilm 14, it is not oxidized. As the densifying process, not only aprocess performed by an ordinary furnace but also rapid thermal anneal(RTA) may be used. In the RTA, thermal treatment performed at a highertemperature, e.g., 900° C. for about 20 seconds can be used.

In the heating step, the heat treatment cannot be carried out at ahigher temperature than 850° C. for a long time. This is because anoxidant is diffused into edges of the tunnel oxide film to form awedge-shaped oxide film called bird's beak. More specifically,densification of the PSZ film is limited because an operatingtemperature is limited, and an etching rate which is almost equal tothat of a thermal oxide film or an HDP film cannot be realized atpresent.

As described above, after the PSZ film is transformed into the SiO₂(silica) film, planarization is performed by a CMP method. When a CMPpolishing agent (slurry) containing colloidal silica as a base is used,50 or more can be realized as an etching selectivity between the PSZfilm and the SiN film 14.

As shown in FIG. 4G, an etching back process is performed under acondition under which the filled PSZ film can be completely removed. Anetching selectivity between the HDP film and the PSZ film is desirably2.5 or more. At this time, the HDP film on the floating gate side wallmay be slightly left due to a difference between the etching rates ofthe HDP film and the PSZ film, but it may not pose any problem. However,it is difficult to control the level position of STI while removing theremaining HDP film on the floating gate side wall.

That is, since the level position of STI filling at a width of 90 nm isclose to the tunnel oxide film 11, the level position is already lowerthan a desired level position of STI. Furthermore, if protection fromthe chemical from the tunnel film edges is also considered, STI fillingat the desired level position cannot be easily realized by only the HDPfilm serving as the first layer.

Therefore, as shown in FIG. 4G, after the silica film 191 is removed bywet etching to form a second recessed portion 20, as shown in FIG. 4H, asecond HDP film 21 is deposited by an HDP-CVD method. Thereafter, asshown in FIG. 4I, a step coverage on the surface is planarized by a CMPmethod using the SiN film 14 as a stopper, and then a heat treatment iscarried out at about 850° C. in an inert gas atmosphere for one hour. Asa result, the HDP films 18 and 21 are densified to be HDP films 182 and211, respectively, and the STI structure is uniformly filled with theseHDP films.

As shown in FIG. 4J, the HDP film 211 is etched back by ahydrogen-fluoride-based (HF) chemical solution to lower the fillinglevel to a desired level. Thereafter, as shown in FIG. 4K, the SiN film14 is removed by a hot phosphoric acid. As a result, good planarity andpreferable level controllability of the surface of the filled HDP filmin the STI structure can be provided to realize a desired STI shapewhich suppresses a variation in a coupling ratio.

Thereafter, as shown in FIG. 4L, the ONO film 22, the control gateelectrode 23, and the interlayer insulating film 24 are formed. Althoughthe subsequent steps are not shown, continuously, contacts, wiringlayers, a passivation film, pads, and the like are provided to completean NAND flash memory.

As is apparent from the above explanation, in the first embodiment, asshown in FIGS. 4F and 4G, after planarization is performed by using thePSZ film as a sacrificial film, the PSZ film is selectively removed tomake the aspect ratio more moderate than the aspect ratio of the trench17. When the silica film 191 transformed from the PSZ film isselectively removed, the peripheral HDP film 18, i.e., a part of the HDPfilm 18 is isotropically etched to increase the opening of the firstrecessed portion 181, thereby forming the second recessed portion 20. Asa result, the aspect ratio is further improved. As shown in FIG. 4H, thesecond HDP film 21 is formed, and then the surface of the HDP film 21 isplanarized again outside and above the STI. Therefore, the STI fillingmaterial surface can be planarized with good controllability.

A process for manufacturing an STI structure of 70-nm generation will bedescribed below. In the 90-nm generation described above, the level ofthe first HDP film on the STI bottom is higher than that of theinterface of the tunnel insulating film 11. However, in the STIstructure having a width of 70 nm or less, as shown in FIG. 4M, thelevel of the first HDP film is generally lower than that of theinterface of the tunnel oxide film 11.

Furthermore, as described in FIGS. 4D-4F, a coating film 19 is formedand transformed into a silica film 191 by a densifying process, and thesilica film 191 is planarized by the CMP method or the like. Thereafter,in order to control the level of the filled film in the STI trench, wetetching is performed.

In this case, the PSZ film used in filling may be left without beingcompletely removed in wet etching. More specifically, as shown in FIG.4N, the silica film 191 transformed from the PSZ film is partially left.Thereafter, as shown in FIG. 4O, the second HDP film 21 is filled in theSTI to realize a structure in which the silica film 191 is included inthe HDP film.

According to the manufacturing method described above, filling of theHDP film can be realized for an NAND-STI structure of 90-70-nm-widthgeneration or later. A drawback such as a wet etching rate differencecaused by using different materials in uncontrollable adjustment of anSTI filling level can be eliminated. Therefore, a production yield canbe considerably increased.

A second embodiment will be described below. In the first embodiment,the PSZ film is used as the coating type insulating film. However, apolymer material such as a photoresist film or a material which ischanged into an inorganic material after a hardening process by curingcan be used. The same reference numerals as in the first embodimentdenote the same parts in the second embodiment.

More specifically, when a coating film is formed as shown in FIG. 4E, aphotoresist film is used for the STI structure of 90-nm generation shownin FIG. 4D as a coating material. After the photoresist film is coated,a baking process at 120° C. for about 30 seconds is performed. In thismanner, a solvent remaining in the photoresist film is vaporized to makeit possible to harden the film, or the film is polymerized by generatingcross-linkage by light irradiation to make it possible to harden thefilm.

As in FIG. 4F, surface polishing is carried out by a CMP method using anSiN film 14 as a stopper. Thereafter, ashing is performed at 150° C. for30 seconds in an O₂ atmosphere to remove a photoresist film partiallyfilled in the STI. Furthermore, the resultant structure is cleaned byoxidizing acid treatment using a sulfuric acid or the like to removeresidue.

As a result, a structure as shown in FIG. 5A is obtained although anopening 30 is narrower than that in FIG. 4G. When an aspect ratio whichis almost equal to that of the opening 30 is used, an HDP film can befilled. For this reason, as shown in FIG. 5B, an HDP film 21 is filled.The subsequent steps are the same as those in the steps subsequent tothe step in FIG. 4H in the first embodiment. Finally, a structure shownin FIG. 4L is provided.

This method can be similarly applied to an STI structure of 70-nmgeneration. More specifically, as shown in FIGS. 4M and 4N, even thoughthe level position of the STI bottom is lower than the interface of thetunnel insulating film 11, similarly, a material such as a photoresistis coated, and a baking process and a planarizing process by a CMPmethod are performed. Furthermore, the ashing process and the cleaningprocess using a sulfuric acid or the like are performed. At this time,since the HDP film 18 is densified by the curing process, dissolutioncaused by an acid rarely occurs. Therefore, as shown in FIG. 5C, thephotoresist film can be completely removed by the acid treatment.

In this case, since the aspect ratio of an opening 31 increases, thesecond HDP film 21 cannot be easily filled. Therefore, as shown in FIG.5D, the opening is etched by an RIE method or the like to increase theopening, thereby forming a structure of a bowl-shaped STI bottom. In anopening 32 obtained in this manner, the second HDP film 21 can befilled. For this reason, as in the case shown in FIG. 5B, an STIstructure in which the second HDP film 21 is filled can be obtained.

The subsequent steps are the same as the steps subsequent to the step inFIG. 4H in the first embodiment. Finally, a structure shown in FIG. 4Lcan be formed. A structure in which a coating film is included in theHDP film filled in the STI as shown in the case of FIG. 4O can besimilarly obtained. At this time, as the coating film, a film which ischanged into an inorganic material free from carbon after the hardeningprocess by curing is desirably used.

As described in the first embodiment or the second embodiment, the PSZfilm (silica film) or the inorganic material film included in the HDPfilm filled in the STI acts as a buffer film which moderates stress inthe STI to make it possible to suppress drawbacks such as cracks or filmpeeling.

A third embodiment will be described below. The same steps as in thefirst embodiment will be omitted, and only characteristic steps will bedescribed below. The same reference numerals as in the first embodimentdenote the same parts in the third embodiment. In FIGS. 4F and 4G, thecoated PSZ film 19 is transformed into a silica film 191 by applying ahardening process to the PSZ film 19. Thereafter the silica film 191 isremoved by wet etching.

In this embodiment, as shown in FIGS. 6A to 6C, after the PSZ film 19 isdeposited and transformed into the silica film 191 by the heattreatment, the silica film 191 is directly etched back by a dry processsuch as an RIE method or the like to a level position where the silicafilm 191 is completely removed. Thereafter, as shown in FIG. 4H, asecond HDP film 21 is provided. In this manner, the steps ofplanarization and wet etching in FIGS. 4F and 4G can be omitted.

Furthermore, a fourth embodiment will be described below. The same stepsas in the first embodiment will be omitted, and only characteristicsteps will be described below. The same reference numerals as in thefirst embodiment denote the same parts in the fourth embodiment. Morespecifically, as shown in FIG. 4D in the first embodiment, after the HDPfilm 18 is deposited, the CMP step is directly carried out withoutperforming the coating step of the PSZ film or the like as it is asshown in FIG. 7A in the fourth embodiment.

At this time, as a CMP polishing agent (slurry), acolloidal-silica-based agent containing a small amount of additive suchas sodium (Na) is selected. When this CMP process is performed, as shownin FIG. 7A, a slurry 41 is inserted into an incomplete filling trench 40of the HDP film and remains therein.

However, since the slurry 41 is provided by single particles containinghydrated silica as a main component, it can be easily dissolved by abuffered hydrofluoric acid. At this time, a ratio of the etching rate ofthe slurry 41 to the etching rate of the HDP film around the trench isabout 5 or more because the slurry is granular and has a wide etchingarea and because the film quality of the HDP film is closer to the filmquality of a thermal oxide film than that of the slurry. In addition,since a small amount of additive is selected as the additive such as Na,as shown in FIG. 7B, the additive can be removed by water washing. As aresult, a structure having a second recessed portion 20 as shown in FIG.7C is provided. The resultant aspect ratio is more moderate than theaspect ratio of the recessed portion in the HDP film. Since thesubsequent steps are the same as those in the first embodiment, adesired STI structure as shown in FIG. 4K is obtained.

A case in which the slurry 41 is allowed to remain in the incompletetrench 40 of the HDP film will be described below. More specifically,after the additive in the slurry is removed by an appropriate acid orwater washing, as shown in FIG. 4H, a second HDP film 21 is formed onthe structure in which the HDP film and the residue are filled. In aprocess in which subsequent annealing to densify these oxide films isperformed, the particles of the slurry residue are melted to form aporous region. As a result, as shown in FIG. 7D, like the silica film inFIG. 4O, a filling structure of the HDP film 21 including a crystallizedporous film 42 is obtained.

The characteristic features of the structure described above will bedescribed below. More specifically, when a PSZ coating film having alarge thermal contraction is used, for example, when a PSZ film remainsas a film included in the STI, the PSZ film is not a porous film after aheat treatment to generate tensile stress to the silicon substrate andthe floating gate portion which are adjacent to the PSZ. As a result,dislocation and point defects are caused in the silicon film. In theworst case, the filled film in the STI may be cleaved in the verticaldirection. In the first embodiment (FIG. 4O), the cleavage does notoccur because the region of the PSZ film (silica film) is narrow.However, with scaling down of the STI structure, the occupied area ofthe coating film in the STI increases to make these problems serious.

However, the porous region formed by using the slurry as a material actsas a buffer film which moderates the internal stress in the STI to makeit possible to suppress drawbacks such as defects and cleavage. Thecoating solution is a coating solution for forming a silica-basedcoating film or the like, and is not limited to PSZ.

The aspect of the embodiments are as follows.

(1) The coating solution is a coating solution for forming asilica-based coating film or the like, and is not limited to PSZ.

(2) Heat treatment is carried out in an oxidizing atmosphere or an inertgas atmosphere to perform a process of densifying the HDP film formed asthe lower layer and a process of discharging NH₃, H₂O, and the likeremaining in the SiO₂ film obtained by changing the PSZ film formed asthe upper layer, so that these films are changed into SiO₂ films havinghigher densities.

(3) After the coating film is transformed into the second insulatingfilm, the second insulating film is etched back by an RIE method.Thereafter, a second HDP film is formed.

(4) As the coating film, a material such as a photoresist film which ischanged into an inorganic material after a hardening process by curingis coated and then applied with a baking process.

(5) The filled photoresist film is removed by an ashing process.

(6) The level of the planarized surface is higher than the levelposition of the tunnel oxide film.

(7) In 70-nm-width generation or later, the level of the polanarizedsurface is lower than the level position of the tunnel oxide film.

(8) The first and second HDP films are formed and applied with heattreatment in an inert gas atmosphere to densify the HDP films.

(9) The second HDP film is filled in the STI such that the silica filmis partially left, thereby obtaining a structure in which the silicafilm is included in the HDP film.

(10) After additive in the slurry is removed by an acid or waterwashing, the second HDP film is formed on a structure in which the HDPfilm and the residue are buried. In the subsequent heat treatmentprocess to densify these oxide films, a filling structure of the HDPfilm including a porous film which is formed such that the particles ofslurry residue are melted and then crystallized is obtained.

(11) At least a part of the porous inorganic film included in the HDPfilm acts as a buffer film which moderates the internal stress of theSTI.

(12) Water washing is performed before the slurry remaining in therecessed portion is removed by a chemical solution to removewater-soluble impurities.

(13) The porous film is formed by melting the particles of the slurryresidue.

(14) The method described above is applied to STI filling of a flashmemory or a CMOS logic product.

Additional advantages and modifications will readily occur to thoseskilled in the art. Therefore, the invention in its broader aspects isnot limited to the specific details and representative embodiments shownand described herein. Accordingly, various modifications may be madewithout departing from the spirit or scope of the general inventiveconcept as defined by the appended claims and their equivalents.

1.-8. (canceled)
 9. A method of manufacturing a semiconductor device comprising: forming a trench in a semiconductor substrate; forming a first insulating film having a recessed portion in the trench; planarizing an upper side of the first insulating film by a CMP method using a slurry; removing at least the slurry remaining in the recessed portion of the first insulating film by a chemical solution to moderate an aspect ratio for the recessed portion formed in the first insulating film; and forming a second insulating film on a surface of the semiconductor substrate so as to fill the recessed portion therewith.
 10. The method according to claim 9, wherein the slurry is comprised of a single particle containing hydrated silica as a main component.
 11. The method according to claim 9, wherein the first insulating film is comprised of an HDP film.
 12. The method according to claim 9, wherein the second insulating film is constituted by an HDP film.
 13. The method according to claim 9, wherein an annealing process is carried out after the second insulating film is formed. 14.-17. (canceled) 